ABSTRACT
This paper presents the basic assumptions of the concept of a new technology for the valorisation of chromium tannery waste. It assumes the use of an integrated system of the thermal pressure hydrolysis process and membrane filtration techniques for the recovery of chromium compounds and the use of a separated organic matter during anaerobic fermentation. According to the assumptions of the developed technological concept, at the first stage, the crushed mixture of chromium tannery waste is decomposed in the process of thermal pressure hydrolysis using appropriate process conditions in an alkaline environment. Then, the liquid product of this process (the so-called hydrolysate) is processed using centrifugal force separation and ultrafiltration. Such activities enable the recovery of chromium compounds for rawhide currying and concentration of organic matter (fats, proteins) with energy potential. Research carried out under conditions similar to real operating conditions proved that chromium compounds recovered from waste can be successfully used in the processing of cowhides intended for the production of footwear. The industrial implementation of the developed technology for valorising chromium tannery waste would enable the transition from a linear to a circular economy.
ABSTRACT
This paper presents the results of research on a new method of chromium recovery from solid waste generated during the tanning of raw hides. In the first stage, the shredded mixture of useless leather scraps is decomposed through thermal pressure hydrolysis (TPH) in nitric acid in appropriate process conditions. Then, the liquid product of this process (hydrolysate) is fractionated using membrane separation techniques. The microfiltration (MF) process enables the initial purification of the hydrolysate by concentrating the organic matter. On the other hand, the nanofiltration (NF) process enables a three-fold concentration of total chromium in the pre-purified hydrolysate. The total chromium concentrate prepared in the above manner was successfully used in the model tanning processes. These processes were carried out on pickled bovine hides, using a mixture of a commercial chromium tanning agent and chromium concentrate after nanofiltration. The reference sample was bovine hide traditionally tanned with a commercial chromium tanning agent. Based on the results of the physical and chemical analyses, it was found that the properties of hides tanned using chromium recovered from waste are similar to those of hides tanned traditionally using a commercially available chromium tanning agent. The industrial implementation of the developed tannery waste valorisation technology would enable transition from a linear economy to circular economy.
ABSTRACT
The 2:1 sandwich-type complexes formed between a cyclopeptide with alternating L-proline and 6-aminopicolinic acid subunits and inorganic anions can be stabilized by covalently linking a tris-alkyne and a tris-azide derivative of this peptide through copper-catalyzed azide-alkyne cycloaddition. The resulting triply linked bis-cyclopeptide can interact with anions such as sulfate ions in aqueous solution by including them into the cavity between the two cyclopeptide rings, where they can form hydrogen bonds to amide NH groups, distributed along the inner surface. The binding kinetics of this system differ significantly from those of a bis-cyclopeptide that contains only one linker because the rate of guest exchange is considerably slower. Thermodynamically, the stability of the sulfate complex of the triply linked bis-cyclopeptide approaches a log K(a) value of 6 in H(2)O/CH(3)OH 1:1 (v/v) which is, however, only approximately one order of magnitude larger than affinity of the more flexible monolinked analogue. Titration calorimetry revealed that this behavior is mainly due to the change in the binding enthalpy from exothermic to endothermic upon increasing the number of linkers. Results from NMR spectroscopy and X-ray crystallography indicate that the mono- and triply linked bis-cyclopeptides adopt similar conformations in their complexes with sulfate ions, but the complex formation is enthalpically unfavorable for the cage. The substantial entropic contribution to sulfate complexation of this receptor more than compensates for this disadvantage, so that the overall sulfate affinity of both bis-cyclopeptides ends up in the same range. These investigations provide important insight into the structure-property relationships of such receptors, thus leading the way to further structural improvement.
